KR101899309B1 - Manufacturing method of retroreflective material containing phosphorescent property - Google Patents

Abstract

The present invention relates to a method for manufacturing a retro-reflective material, and more particularly, to a method for manufacturing a retro-reflective material excellent in luminous efficiency and luminous intensity by using a phosphorescent pigment which does not emit radioactive material. The phosphorescent glass beads manufactured according to the present invention have phosphorescent properties while having excellent brilliance at night to be used in various fields such as a road signage and the like.

Description

[0001] The present invention relates to a manufacturing method of retroreflective material containing phosphorescent material,

The present invention relates to a method for producing a retroreflective material, and more particularly, to a method for producing a retroreflective material by using a phosphorescent pigment that does not emit a radioactive material, such as glass beads (BaO-ZnO-Al (OH) 3-TiO2) To a method for manufacturing a retroreflective material.

The photostimulable glass beads produced according to the present invention have excellent luminosity at night and can be used in various fields such as road signage since they have photostability.

BACKGROUND ART Conventional glass beads (glass beads) are widely used in various industrial materials, and typical uses are widely used for road signs, lanes on roads and other traffic safety related products.

BACKGROUND ART Conventionally, such road signboards or traffic safety related products are mostly formed by attaching a reflective sheet to a visible surface. In addition, glass beads used in lanes on the road are widely used in the form of spraying directly on the coating film in the field construction.

Phosphorescent pigment refers to a pigment that absorbs and scatters light from almost all light sources, including sunlight and light, and emits light slowly in a dark place. It is widely used in the fields of construction, roads, etc. .

As the phosphorescent pigments that are generally used, sulfide-based fluorescent pigments such as ZnS: Cu, Cas: Bi, (Ca, Sr) S: Bi and (Zn, Cd) S: Cu are mainstream. However, sulfide-based phosphorescent pigments are very unstable due to moisture and carbon dioxide in the air, resulting in poor durability and use of environmentally regulated substances such as cadmium (Cd) is limited. Accordingly, studies on oxide-based phosphorescent materials that are excellent in afterglow characteristics and stable both chemically and environment are underway.

It is known that SrAl2O4: Eu2 + and Dy3 + phosphorescent pigments have the best afterglow characteristics and chemical stability in the visible light region among the reported oxide phosphorescent materials. In addition, SrAl2O4: Eu2 +, Dy3 + phosphorescent pigments have a stuffed tridymite structure and are attributed to the 4f-5d transition of the Eu2 + ion, which is an activator added to the SrAl2O4 parent crystal, Dy3 +

(Trap) phenomenon of a hole due to the presence of a hole. In addition, SrAl2O4: Eu

2+ and Dy 3+ phosphorescent pigments exhibit yellow-green color upon emission, and phosphorescence characteristics are known to be greatly influenced by synthesis and use conditions.

Furthermore, there is a growing demand for the use of phosphorescent pigments capable of developing colors under various conditions in ceramics, tiles, and other ceramics products requiring high-temperature manufacturing processes.

Conventional phosphors such as calcium and zinc sulfides which emit phosphorescence were not suitable for labeling in the outside of the room due to their low light-emitting time and light-fastness in a place with high humidity. In order to improve this, mixing the radioactive material such as Pm (promethium) can increase the luminescence duration, but there is a disadvantage that the use of radioactive material is restricted.

As a prior art related to this, Patent Document 1 discloses "a phosphorescent pigment composition having a long afterglow time" which is prepared by mixing SrAl 2 O 4 having a luminescent color of green color and Sr 4 Al 4 O 25 having a luminescent color of 2: 1 and having a color tone of green However, this technique has a long afterglow time, but it has a short time and is unsatisfactory and has a weak alkalinity.

The following Non-Patent Document 1 identifies the change of the phosphorescence characteristics of the SrAl2O4: Eu2 + and Dy3 + phosphors according to the heat treatment conditions at high temperature and examines the causes thereof. Especially, the heat treatment conditions at high temperature (1250 ° C) (Oxidation) atmosphere and a reducing atmosphere heat treatment condition using LPG gas, SrAl2O4: Eu2 +, Dy

3+ phosphors can be used in various applications such as heat-resistant products and ceramic products.

In order to solve the problems of the conventional phosphorescent material, a technique of a phosphorescent pigment in which persistence for a long period of time is maintained even in an alkaline state has been developed by the present inventor and disclosed in Patent Document 2 (JP-A No. 10-1689989, A method for producing this excellent phosphorescent pigment), the content of which is hereby incorporated by reference in its entirety.

The inventor of the present invention has focused on the fact that a glass bead used for retro-reflection purposes and a phosphorescent pigment containing a certain light and exhibiting afterglow property can be usefully used for a paint sign etc. The invention was invented. In other words, by coating the glass bead with phosphorescent pigment, it is coated with paints, applied between the deliner (reflector) and the undelayed section, etc., thereby improving operator's attention and improving visibility, The present invention provides a condensed glass bead having a high crystallinity.

Korean Patent Registration No. 10-0598144, a phosphorescent pigment composition having a long afterglow time Japanese Patent Application Laid-Open No. 10-1689989, entitled " A method for producing a phosphorescent pigment excellent in afterglow.

 Journal of the Korean Ceramic Society "A Study on the High Temperature Stability of SrAl2O4: Eu2 +, Dy3 + Phosphorescent Pigments" 51 (6), 618-22, 2014.

Accordingly, an object of the present invention is to provide a method for producing a glass bead (BaO-ZnO-Al (OH) 3-TiO2) having excellent luminous efficiency and luminous intensity by using a phosphorescent pigment that does not emit radioactive materials.

Another object of the present invention is to provide a retroreflective material having excellent brightness at night and having condensing properties.

It is another object of the present invention to provide a condensing glass bead capable of securing visibility at night due to light phosphorescence ability as well as improving attention and visibility of a driver by coating the space between a deliner (reflector) and a delegator- .

A method for producing a retroreflective material containing a photostabilizing agent according to the present invention comprises

6) a sixth step of preparing a phosphorescent pigment;

7) a seventh step of mixing the phosphorescent pigment obtained in the sixth step with a glass bead component to prepare a slurry state;

8) an eighth step of dispersing the slurry in the seventh step by a ball mill;

9) drying the slurry dispersed in the eighth step;

10) sintering the slurry dried in the ninth step; And

11) crushing the sintered slurry of the tenth step.

Here, the phosphorescent pigment includes

1) 33.8 to 41.6 parts by weight of aluminum hydroxide (H ₃ AlO ₃ ), 2.0 to 3.4 parts by weight of boric acid (H ₃ BO ₃ ), and 0.02 parts by weight of europium oxide (Eu ₂ O ₃ ) were added to 29.3 to 38.5 parts by weight of isopropyl alcohol (IPA) 0.2 to 1.0 part by weight of dysprosium oxide (Dy ₂ O ₃ ), 15.7 to 24.0 parts by weight of strontium carbonate (SrCO ₃ ), 0.004 to 0.91 part by weight of neodymium oxide (Nd ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ) 0.01 to 1.22 parts by weight, and then dispersing the mixture using a ball mill to obtain a slurry state;

2) a second step of drying the slurry dispersed in the first step;

3) a third step of finely pulverizing the slurry dried in the second step uniformly;

4) a fourth step of putting the particles of the third step into a gas furnace and then leaving them to obtain a pigment;

5) a fifth step of immersing the silane compound in the pigment obtained in the fourth step and then drying to obtain a silane-coated phosphorescent pigment; And

Separating the phosphorescent pigment obtained in the fifth step into a filter body.

According to the present invention, it is possible to manufacture glass beads (BaO-ZnO-Al (OH) 3-TiO2) having excellent luminous efficiency and luminous intensity by using a phosphorescent pigment that does not emit radioactive materials.

In addition, it is possible to manufacture retroreflective materials having excellent luminance at night and having condensing properties, and it is possible to improve the attention of the driver and improve the visibility by coating the area between the deliner (reflector) and the delegator, A condensing glass bead capable of securing visibility is provided.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in detail with reference to the drawings.

A method for producing a retroreflective material containing an accumulative property according to the present invention comprises:

It can be divided into two stages,

- Preparation of phosphorescent pigments with excellent afterglow characteristics and

- It is the process of coating (making) phosphorescent pigment on retroreflective material (glass bead).

Of phosphorescent pigment  Produce

First, a method for producing a phosphorescent pigment excellent in afterglow characteristics is described in Patent Document 2 developed by the present inventor, and the content of the document is cited below.

The method for producing a phosphorescent pigment excellent in afterglow characteristics is as follows: 1) 33.8 to 41.6 parts by weight of aluminum hydroxide (H ₃ AlO ₃ ) and 2.0 to 3.4 parts by weight of boric acid (H ₃ BO ₃ ) are added to 29.3 to 38.5 parts by weight of isopropyl alcohol (IPA) , europium _{(Eu 2 O 3) 0.02 ~} 1.4, dysprosium oxide _{(Dy 2 O 3) 0.2 ~} 1.0 parts by weight, strontium carbonate (SrCO ₃₎ 15.7 ~ 24.0 parts by weight, neodymium (Nd ₂ O ₃₎ oxide 0.004 ~ 0.91 oxide And 0.01 to 1.22 parts by weight of yttrium oxide (Y ₂ O ₃ ) are mixed and dispersed using a ball mill to obtain a slurry state; 2) a second step of drying the slurry dispersed in the first step; 3) a third step of finely pulverizing the slurry dried in the second step uniformly; 4) a fourth step of putting the particles of the third step into a gas furnace and then leaving them to obtain a pigment; 5) a fifth step of immersing the silane compound in the pigment obtained in the fourth step and then drying to obtain a silane-coated phosphorescent pigment; 6) separating the phosphorescent pigment obtained in the fifth step into a filtrate.

First, in the first step, 33.8 to 41.6 parts by weight of aluminum hydroxide (H ₃ AlO ₃ ), 2.0 to 3.4 parts by weight of boric acid (H ₃ BO ₃ ), and europium (Eu ₂ O ₃ ) are added to 29.3 to 38.5 parts by weight of isopropyl alcohol O ₃ ) of 0.02 to 1.4, dysprosium oxide (Dy ₂ O ₃ ) of 0.2 to 1.0 weight part, strontium carbonate (SrCO ₃ ) of 15.7 to 24.0 weight parts, neodymium oxide (Nd ₂ O ₃ ) of 0.004 to 0.91 weight part, yttrium oxide Y ₂ O ₃ ) are added at the same time and dispersed using a ball mill to obtain a slurry state. As the kind of the ball mill, a zirconium ball mill is used, and 7 kinds of liquid such as isopropyl alcohol and solid aluminum hydroxide are simultaneously mixed and dispersed to make a slurry state. At this time, dispersion of the mixed mixture can be performed at a rate of 100 to 500 rev / min for 0.5 to 5 hours.

The second step is to dry the dispersed slurry in the first step, and the drying is preferably performed in an oven at 75 to 120 ° C for 24 to 48 hours.

In the third step, the slurry dried in the second step is homogeneously pulverized into particles. A fine grinder such as a homogenizer can be used for the fine grinding, and the average particle size of the slurry can be made 10 to 100 mu m by fine grinding. At this time, when the average particle diameter is 10 μm, the time and energy consumption due to the fine pulverization can be increased. When the average particle diameter is more than 100 μm, the coating of the silane compound may not be performed well.

In the fourth step, the particles of the third step are put into a gas furnace and then left to obtain a pigment. 90 to 98% by volume of nitrogen (N ₂ ), 1 to 8% by volume of hydrogen (H ₂ ) and 1 to 5% by volume of other gases are introduced into the gas furnace and the particles are heated at 700 to 1700 ° C. for 1 to 6 hours The pigment can be obtained. At this time, europium (Eu) is reduced (Eu ^{2 +} -> Eu ^{3 +} ) by yttria (Y ₂ O ₃ ) and neodymium oxide (Nd ₂ O ₃ ) in the gas furnace.

In the fifth step, the silane compound is immersed in the pigment obtained in the fourth step, followed by drying to obtain a silane-coated phosphorescent pigment. The phosphorescent pigment may be surface-modified by mixing the pigment with the silane compound at 95 to 98: 5 to 2 parts by weight, immersing the pigment for 1 to 2 hours, and drying at 75 to 100 ° C for 4 to 12 hours. (Z-6121 SILANE product of Dow Corning), vinyl silane (Z-6518 SILANE product of Dow Corning), epoxy silane (Z-6040 SILANE product of Dow Corning), methacryl silane Z-6030 SILANE product), alkylsilane (Z-6582 SILANE product of Dow Corning), and phenyl silane (Z-5314 SILANE product of Dow Corning).

Finally, in the sixth step, the phosphorescent pigment obtained in the fifth step is separated into a filter body. The phosphorescent pigment is separated into a filtrate and a final product having a size of 5 to 100 탆 can be obtained.

The preparation of the phosphorescent pigment of the present invention includes the following steps: 1) Dysprosium oxide (Dy ₂ O ₃ ), neodymium oxide (Nd ₂ O ₃ ) (Y ₂ O ₃ ) content, 2) the milling time of the pigment is controlled from 30 minutes to 1 hour, the color difference and the afterglow intensity are different due to the difference in crystallinity, and 3) the temperature To less than 900 DEG C, and the like.

The preparation of blue phosphorescent pigments is carried out in the following manner: 1) the content of dysprosium oxide (Dy ₂ O ₃ ), neodymium oxide (Nd ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ) 5 hours, there is a difference in color and afterglow strength, and 3) the temperature of the gas is set to 900 ° C or higher.

Phosphorescent pigment  Mixed Glass bead  Produce

The glass beads have components of Al (OH) ₃ , BaO, ZnO and TiO _{2. When} the prepared glass beads themselves are mixed with the phosphorescent pigment, coating of the phosphorescent pigment is impossible. Accordingly, the present inventors manufactured the glass beads mixed with the phosphorescent pigment by mixing the pigments in the production of the glass beads. On the other hand, the sintering process of the glass beads is carried out at a high temperature, usually 900 to 1200 ° C. At this temperature, the accumulation of ordinary phosphorescent pigments disappears. The inventors of the present invention have found that the use of special pigments I solved this.

3 to 5 parts by weight of IPA, 20 to 25 parts by weight of Al (OH) ₃ and 19 to 21 parts by weight of BaO based on the total weight of the slurry + phosphorescent pigment mixture. 20 to 25 parts by weight of ZnO and 20 to 28 parts by weight of TiO ₂ are simultaneously added to prepare a slurry. 0 to 10 parts by weight of the above-prepared phosphorescent pigment is used to prepare a glass bead mixed with a phosphorescent pigment.

When the amount of IPA is less than 3 parts by weight, it is difficult to form a slurry. When the amount of IPA is more than 5 parts by weight, the mixing viscosity and thixotropy are lowered and the mixing property between powders is decreased. When the amount of Al (OH) ₃ is 20 parts by weight, the chemical bonding between the glass beads and the phosphorescent pigment decreases. When the amount of Al (OH) ₃ is more than 25 parts by weight, , Retroreflection is reduced, and when it is more than 21 parts by weight, it has little effect on the increase of the luminance value. When the content of ZnO is 20 parts by weight or less, the strength of the phosphorescent glass bead is lowered. When the content is 25 parts by weight or more, the increase in strength is insufficient. When the amount of TiO _{2 is} 20 parts by weight or less, the luminance value is remarkably lowered. When the amount is 20 parts by weight or more, the strength of the phosphorescent glass decreases. When the amount of the phosphorescent pigment is 10 parts by weight or more, the retroreflectivity of the light source is remarkably decreased and the luminance value is decreased.

The mixture of the glass bead composition and the phosphorescent pigment is dispersed in a ball mill at a rate of 100 to 500 rev / min for 0.5 to 5 hours to form a slurry state. The dispersed slurry is agitated in an oven at 75 to 120 ° C for 24 to 48 hours Dry. The dried slurry is sintered at 900 to 1200 ° C. and pulverized to obtain a condensed glass bead of BaO-ZnO-Al (OH) 3 -TiO 2 type in which a phosphorescent pigment is finally coated.

( Manufacturing example  1) Green Phosphorescent pigment  Produce

1) To 303 g of isopropyl alcohol (IPA), 337 g of aluminum hydroxide {Al (OH) ₃ }, 34 g of boric acid (H ₃ BO ₃ ), 11 g of europium oxide (Eu ₂ O ₃ ), 7 g of dysprosium oxide (Dy ₂ O ₃ ) 248 g of strontium carbonate (SrCO ₃ ), 5 g of neodymium oxide (Nd ₂ O ₃ ) and 10 g of yttrium oxide (Y ₂ O ₃ ) were simultaneously introduced into a zirconium ball mill and dispersed at a rate of 300 rev / min for 1 hour to form a slurry.

2) The slurry was dried in an oven at 120 ° C. for 48 hours and then homogenized to a size of 10 to 100 μm using a homogenizer.

3) The pulverized slurry was charged into a gas filled with a gas mixed with nitrogen, hydrogen and the like, and then left at 800 ° C for 4 hours to obtain a pigment.

4) Subsequently, 5 g of aminosilane (manufactured by Dow Corning Z-6121 SILANE) was added to 95 g of the obtained pigment, and the resulting pigment was immersed for 1 hour and dried in an oven at 100 ° C. for 4 hours to obtain a phosphorescent pigment coated with silane on the surface, The pigment was separated into a particle size of 5 to 100 mu m with a filtrate to obtain a final green product.

( Manufacturing example  2) Accumulation Glass bead  Produce( Example  1-3)

The phosphorescent pigment prepared in Preparation Example 1 was mixed with the constituents of each glass bead to prepare a slurry state according to the content of Table 1, and the slurry thus prepared was dispersed in a ball mill at a rate of 300 rev / min for 5 hours Respectively. The dispersed mixture was dried in an oven at 120 DEG C for 35 hours. The dried powder was sintered at 1200 ° C and then pulverized to a size of 10 to 100 μm in average particle size of the slurry in a homogenizer mill so that the glass beads due to pyrolysis of Al (OH) Light glass beads were prepared.

No. Constituent Glass bead
(wt%) Example 1 (wt%) Example 2 (wt%) Example 3
wt (%) One IPA 3.42 3.57 3.42 3.24 2 Al (OH) 3 22.22 23.15 22.20 21.04 3 BaO 20.38 21.23 20.36 19.30 4 ZnO 23.19 24.16 23.17 21.96 5 TiO2 25.79 26.88 25.78 24.43 6 Phosphorescent pigment
(Production Example 1) 0.00 1.01 5.06 10.02 system 100 100 100 100

The luminance and the afterglow time of each of the condensed glass beads prepared as shown in Table 1 were measured and recorded in Tables 2 and 3.

division The luminance value (mcd) Glass bead 1350 Example 1 1300 Example 2 1100 Example 3 800

division Afterglow time (min) The luminance value (mcd) 1 minute 10 minutes 20 minutes Glass bead 0 0 0 0 Example 1 One 50 0 0 Example 2 10 500 100 0 Example 3 20 700 200 10

As shown in Tables 2 and 3, the condensed glass beads produced according to the present invention are expected to be widely used in reflectors having high brightness and excellent afterglow properties and having properties that are excellent at nighttime and visibility

Claims (4)

delete delete delete A method for producing a retroreflective material containing an accumulative property,
6) a sixth step of preparing a phosphorescent pigment;
7) a seventh step of mixing the phosphorescent pigment obtained in the sixth step with a glass bead component to prepare a slurry state;
8) an eighth step of dispersing the slurry in the seventh step by a ball mill;
9) drying the slurry dispersed in the eighth step;
10) sintering the slurry dried in the ninth step; And
11) crushing the sintered slurry of the tenth step,
The step of preparing the phosphorescent pigment in the sixth step includes:
1) 33.8 to 41.6 parts by weight of aluminum hydroxide (H ₃ AlO ₃ ), 2.0 to 3.4 parts by weight of boric acid (H ₃ BO ₃ ), and 0.02 parts by weight of europium oxide (Eu ₂ O ₃ ) were added to 29.3 to 38.5 parts by weight of isopropyl alcohol (IPA) 0.2 to 1.0 part by weight of dysprosium oxide (Dy ₂ O ₃ ), 15.7 to 24.0 parts by weight of strontium carbonate (SrCO ₃ ), 0.004 to 0.91 part by weight of neodymium oxide (Nd ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ) 0.01 to 1.22 parts by weight, and then dispersing the mixture using a ball mill to obtain a slurry state;
2) a second step of drying the slurry dispersed in the first step;
3) a third step of finely pulverizing the slurry dried in the second step uniformly;
4) a fourth step of putting the particles of the third step into a gas furnace and then leaving them to obtain a pigment;
5) a fifth step of immersing the silane compound in the pigment obtained in the fourth step and then drying to obtain a silane-coated phosphorescent pigment; And
6) separating the phosphorescent pigment obtained in the fifth step into a filter body,
The seventh step is a step of blending 20 to 25 parts by weight of Al (OH) ₃ and 19 to 21 parts by weight of BaO as the glass bead component, based on the total weight of the slurry + phosphorescent pigment mixture. 20 to 25 parts by weight of ZnO, 20 to 28 parts by weight of TiO ₂ and 3 to 5 parts by weight of IPA are added simultaneously to prepare a slurry,
In the eighth step, the phosphorescent pigment and the glass bead slurry mixture are dispersed in a ball mill at a rate of 100 to 500 rev / min for 0.5 to 5 hours,
The ninth step is to dry the dispersed phosphorescent pigment and the glass bead slurry mixture in an oven at 75 to 120 DEG C for 24 to 48 hours,
A method for producing a retroreflective material having a photoconductive property with a BaO-ZnO-Al (OH) 3-TiO2 bond, which comprises performing the sintering at a temperature of 900 to 1200 ° C in the tenth step.